2.

BEHAVIOR OF PURE SUBSTANCES

The relationships between pressure, volume, and temperature will be presented for a pure substance. A pure substance is homogeneous. It may exist in more than one phase, but each phase must have the same chemical composition.

2.1

The Equation of State of Ideal Gas

The pressure-volume relationship of a gas at constant temperature was first determined experimentally in 1660 by Robert Boyle: P

1 V

Similarly, the volume-temperature relationship of a gas at constant pressure was first determined experimentally by Charles in 1787:
V T

In 1802 Joseph Gay-Lussac observed

=
where is equal to 1/273.

1 V V o T P

Invention of a hypothetical gas which obeys Boyles's and Charles' laws exactly at all values of temperature and pressure is the ideal gas and equals to 1/273.16, which means that the volume of the ideal gas is zero at -273.16C . This defines an absolute scale of temperature called the ideal gas temperature scale. Combination of Boyle's law and Charles' law gives

PV Po Vo = = constant T To
This constant termed R, universal gas constant, thus, the equation of state of the ideal gas, so-called ideal gas law, is written as PV = RT.

2.2 Deviation from Ideality and Equations of State of Real Gases

For air, fortunately, the ideal-gas equation is surprisingly accurate for a wide range of temperatures and pressures. When the vapor of a substance has relatively low density, pressure, volume, and temperature are related by the simple equation of state of ideal gas. In the ideal gas hypothesis followings are assumed: i) ii) the particle of a gas has no volume there is no interactions between the particles

The deviation of a real gas from ideal behavior can be measured as the deviation of the compressibility factor Z from unity. The compressibility factor Z is defined as

Z=

PV RT

or

PV = ZRT

In the following figure Z is replotted as a function of PR , reduced pressure defined P / Pcr , at several reduced temperatures also defined T R = T / Tcr .

2.3 P-V-T Relationships of Gases

For all gases it is experimentally found that
PV RT 1.

lim it P 0

Thus isotherms, plotted on a P-V diagram, becomes hyperbolic, being given by PV = RT. As the temperature is decreased, the character of the P-V isotherms changes and eventually a value of T = Tcritical is reached. At temperature below Tcr two phases can exist, i.e., vapor and liquid thus coexist in equilibrium.

2.4 Equation of State of van der Waals Gas

For non-ideal gases, especially for weakly interacting gases

a P + 2 ( V b ) = RT V a is a correction term for particle V2 interaction, and b is a correction term for the finite volume of the particles.
where P is the measured pressure of the gas,
Gas He H2 N2 CO O2 CO2 NH3 H2O Tcr (K) 5.3 33.3 126.1 134.0 153.4 304.2 405.6 647.2 Pcr (atm) 2.26 12.8 33.5 35.0 49.7 73.0 111.5 217.7 Vcr (cm3/mole) 57.6 65.0 90.0 90.0 74.4 95.7 72.4 45.0 a (liter2atm/mole2) .0341 .2461 1.39 1.49 1.36 3.59 4.17 5.46 b (cm3/mole) 23.7 26.7 39.1 39.9 31.8 42.7 37.1 30.5 Zcr .299 .304 .292 .295 .293 .280 .243 .184

Another expression of equation of state for non-ideal gas is virial equation of state:

P=

RT B(T ) C(T ) + 2 + 3 +... V V V

2.5

Water Vapor: Steam

Water or water vapor is a pure substance while air is not a pure substance. A substance can exist in three different phases: solid, liquid, and gas. Consider an experiment in which a solid is contained in a piston-cylinder arrangement such that the pressure is maintained at a constant value. If the experiment is repeated a number of times using different pressure, following T- diagram results shown below. At pressures that exceed the pressure of the critical point, the liquid simply changes to a vapor without a constant-temperature vaporization process.

A saturated vapor lies on the saturated vapor line and a saturated liquid on the saturated liquid line. The region to the right of the saturated vapor line is the superheated vapor region; the region to the left of the saturated liquid line is the compressed liquid region (also called the sub-cooled liquid region). A supercritical state is encountered when the pressure and temperature are greater than the critical values. The data obtained in an actual experiment could be presented as a three-dimensional surface with P = P( ,T).

(a)

(b)

(c)

2.6

The Liquid-Vapor Region

At any state (T, ) between saturated points f and g, shown in right figure, liquid and vapor exist as a mixture in equilibrium. Let f and g represent, respectively, the specific volumes of the saturated liquid and the saturated vapor.

Let m be the total mass of a system, mf the amount of mass in the liquid phase, and mg the amount of mass in the vapor phase. m = (mf + mg ) =mf f + mg g The ratio of the mass of saturated vapor to the total mass, x = m g /(m f + m g ) , is called the quality of the mixture. Therefore, we obtained

= f + x( g f )
= f + x fg
where

fg = g f .

Similarly all thermodynamic properties of the mixture of phase i and j can be expressed in the same way:

mixture = i + x( j i ) = i + xij

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EXERCISE PROBLEMS A] Solved Problems 1. Estimate the pressure of NH3 gas at a temperature 300K and a specific

volume of 0.1321 m3/kg using a) the ideal gas equation and b) the vander walls equation. According to the thermodynamic table for superheated ammonia the pressure is 1000 kPa. c) What makes these differences? Ans. a) 1103.5 kPa b) 1038.1 kPa c) NH3 is a radical and big molecule. 2. Suppose that you are going to design a small pressure vessel containing 1 kg of water whose design pressure is 220kPa. If you need a water - steam mixture with quality x = 0.8 inside vessel determine the inside volume of the vessel. Ans. 0.664 m3 3. An automobile tire with a volume of 0.6m3 is inflated to a gage pressure of 200 kPa. Calculate the mass of air in the tire if the temperature is 20 C . Ans. 2.14 kg

B] Unsolved Problems 4. Four kg of water is placed in an enclosed volume of 1m3. Heat is added until the temperature is 150 C . Find (a) the pressure, (b) the mass of vapor, and (c) the volume of the vapor. 5. Water is contained in a rigid vessel of 5 m3 at a quality of 0.8 and a pressure of 2 MPa. if the pressure is reduced to 400 kPa by cooling the vessel, find the mass of vapor mg and mass of liquid m f . 6. Calculate the pressure of steam at a temperature of 500 C and a density of 24kg/m3 using (a) the ideal-gas equation, (b) the van der Waals equation, (c) the compressibility factor, and (d) the steam table. 7. Behavior of hydrogen gas is generally described with van der Waals equation whose constants are a = 0.246 liter2/atm and b = 0.02668 liters. There is 10 moles of 1 atm hydrogen gas at 27oC what is the volume of this hydrogen gas? If this gas is compressed isothermally to 100 atm, calculate the

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final volume after compression a) using the ideal gas law and b) van der Waals equation. 8. A pressurized can contains air at a gage pressure of 0.3 MPa when the temperature is 25 C . The can will burst when the gage pressure reaches 1.5MPa. At what temperature will the can burst? 9. A graduate student has designed a high pressure mini-autoclave for Zirconium alloy cladding corrosion experiment. The inside volume is 100cm3. If he half-fills the autoclave with water and heat the autoclave to 360oC, what is the state (quality) and water-steam mixture pressure of the inside autoclave? 10. Hypothetical thermal rocket is a rocket designed to be launched due to the air volume expansion inside the chamber when the chamber is heated up to high temperature by external heating. A undergraduate student is practicing to design the hypothetical thermal rocket with straight nozzle 100

m in diameter whose chamber inside volume and weight are 0.01 m3 and 1 kg, respectively. If the chamber is instantaneously heated to 4000oC after the ignition what is the acceleration at the moment of launching?

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